WO2023223670A1 - Polymère et composition de résine pour lentille optique - Google Patents

Polymère et composition de résine pour lentille optique Download PDF

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WO2023223670A1
WO2023223670A1 PCT/JP2023/011733 JP2023011733W WO2023223670A1 WO 2023223670 A1 WO2023223670 A1 WO 2023223670A1 JP 2023011733 W JP2023011733 W JP 2023011733W WO 2023223670 A1 WO2023223670 A1 WO 2023223670A1
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formula
group
structural unit
polymer
unit represented
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PCT/JP2023/011733
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Japanese (ja)
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翔太 今井
勲 安達
拓 加藤
利彦 神山
崇洋 坂口
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日産化学株式会社
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Publication of WO2023223670A1 publication Critical patent/WO2023223670A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/0204—Polyarylenethioethers
    • C08G75/0227—Polyarylenethioethers derived from monomers containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses

Definitions

  • the present invention relates to a polymer, a resin composition for an optical lens, and a microlens obtained from the resin composition.
  • An etchback method is known as one of the methods for manufacturing microlenses for CCD/CMOS image sensors (Patent Document 1 and Patent Document 2). That is, a resist pattern is formed on the microlens resin layer formed on the color filter layer, and this resist pattern is reflowed by heat treatment to form a lens pattern. Using a lens pattern formed by reflowing this resist pattern as an etching mask, the underlying microlens resin layer is etched back, and the lens pattern shape is transferred to the microlens resin layer to produce a microlens.
  • lens moldability by dry etching is important.
  • Such lens moldability largely depends on the material of the microlens resin layer.
  • polyphenylene sulfide having a phenolic hydroxyl group certainly has a high refractive index, it is not necessarily a suitable material from the viewpoint of lens moldability. It has been desired to develop a material that exhibits a high refractive index and has excellent lens moldability.
  • the present invention was made based on the above circumstances, and an object of the present invention is to provide a polymer and a resin composition that have both a high refractive index and excellent lens moldability.
  • the present invention provides the following [1] to [11].
  • [1] A polymer containing a structural unit represented by the following formula (1) (excluding the structural unit represented by the following formula (1a)).
  • X independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and n represents an integer of 1 to 6.
  • [2] The polymer of [1], in which n represents 1 in the structural unit represented by formula (1).
  • X represents a methyl or ethyl group.
  • a resin composition for an optical lens comprising (A) the polymer of [1] or [2] and/or a polymer containing a structural unit represented by the following formula (4), and (B) an organic solvent.
  • Component (B) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl lactate, n-butyl lactate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 2-heptanone , cyclopentanone, cyclohexanone, ⁇ -butyrolactone, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone [7] ] Resin composition for optical lenses
  • a resin film containing a polynaphthylene sulfide resin exhibits a high refractive index of 1.75 or more at a wavelength of 550 nm, and forms microlenses with a narrow gap between adjacent lenses by an etch-back method. Is possible.
  • the resin composition for an optical lens of the present invention is characterized by containing a component (A) and a component (B), which will be described later.
  • solid content means components other than the solvent that constitute the resin composition.
  • the polymer of the present invention is not particularly limited as long as it contains a structural unit represented by the following formula (1) (excluding the structural unit represented by the following formula (1a)).
  • X independently represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and n represents an integer of 1 to 6.
  • Examples of the structural units of the polymer include the following formulas (1ba) to (1bn), formulas (1ca) to (1cn), formulas (1da) to (1dn), and formulas (1ea) to (1en). ), and structural units represented by formulas (1fn) to (1fn).
  • Et represents an ethyl group.
  • the proportion of the structural unit represented by the formula (1) (excluding the structural unit represented by the formula (1a)) in the polymer is preferably 10 mol% or more, more preferably 30 mol%. % or more, even more preferably 50 mol% or more, still more preferably 80 mol% or more.
  • X in the formula (1) represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and among them, a methyl group, a methoxy group, and a hydroxy group are preferable, and X represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group. From this point of view, a hydroxy group is particularly preferred. Further, from the viewpoint of ease of synthesis, n in the formula (1) is preferably 1.
  • the molecular weight of the polymer is preferably 500 to 100,000, more preferably 1,000 to 30,000, even more preferably 1,000 as a polystyrene equivalent weight average molecular weight calculated by gel permeation chromatography (GPC). ⁇ 10,000.
  • the polymer can be produced, for example, by applying various known polyarylene sulfide production methods (polycondensation with an aromatic halogen compound and sodium sulfide, oxidative polymerization of an aromatic thiol compound or an aromatic disulfide compound, etc.) to naphthalene derivatives. It can be synthesized by Polymers having hydroxy groups can be synthesized by applying various known polyarylene sulfide production methods to naphthol derivatives with protected hydroxy groups, and then deprotecting some or all of the protecting groups. good.
  • an oxidative polymerization method is preferable, and in particular, from the viewpoint that it can be produced at room temperature and normal pressure without using a metal catalyst, the quinone-based polymer described in Patent Document 5 and Patent Document 6
  • An oxidative polymerization method using an oxidizing agent and an acid is preferably used.
  • a specific method for producing the polymer includes an aromatic thiol compound containing a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group;
  • An example of a method is to perform oxidative polymerization using a quinone oxidizing agent and an acid as a monomer, and then deprotect some or all of the protecting groups.
  • the protected hydroxy group is not particularly limited as long as polymerization proceeds, but from the viewpoint of stability that does not interfere with quinone oxidizing agents or acids, an alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and in the case of a methoxy group is particularly preferable since the deprotection reaction can proceed more easily.
  • the alkoxy group can be converted into a hydroxy group by removing the alkyl group by applying an acid or the like.
  • the acid include trisubstituted boron compounds (boron tribromide, etc.) and Lewis acids such as aluminum chloride, and thiol compounds (dodecanethiol, etc.) and Bronsted acids such as hydrogen bromide. It is not particularly limited as long as it is an acid that can be converted into. All of the protecting groups may be removed or some may remain. Optical properties and solubility can be controlled by appropriately adjusting the deprotection rate.
  • the disulfide monomer represented by the above formula (2) (excluding the disulfide monomer represented by the above formula (2a)) and/or the thiol monomer represented by the above formula (3) (However, the thiol monomer represented by the above formula (3a) is excluded.) can be suitably used.
  • the monomers used in the synthesis of the polymer may be used alone or in combination of two or more. From the viewpoint of adjusting optical properties and solubility in organic solvents, a disulfide monomer not represented by the above formula (2) or a thiol monomer not represented by the above formula (3) may be used as necessary. That is, the polymer only needs to contain at least one kind of structural unit represented by the above formula (1), and may be a homopolymer or a copolymer. When the polymer is a copolymer, its repeating structure is not particularly limited, and it may be any of an alternating copolymer, a block copolymer, a gradient copolymer, and a random copolymer. Moreover, the polymer can be branched depending on the polymerization conditions.
  • Component (A) is a polymer containing a structural unit represented by the above formula (1) (excluding the structural unit represented by the above formula (1a)) and/or a polymer containing a structural unit represented by the above formula (4). It is not particularly limited as long as it is a polymer containing a structural unit. Moreover, other structural units other than the structural unit represented by the formula (1) and the structural unit represented by the formula (4) may be included within a range that does not impair the effects of the present invention. Examples of other structural units include structural units represented by the following formulas (5) to (17).
  • the structural unit represented by the above formula (1) (excluding the structural unit represented by the above formula (1a)) and/or the structural unit represented by the above formula (4) in the component (A)
  • the proportion is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, even more preferably 80 mol% or more.
  • the structural unit represented by the formula (1) has reduced crystallinity due to the presence of the substituent, and therefore is superior to the structural unit represented by the formula (4) from the viewpoint of solubility in organic solvents.
  • X in the formula (1) represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, and among them, a methyl group, a methoxy group, and a hydroxy group are preferable, and X represents a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group. From this point of view, a hydroxy group is particularly preferred. Further, from the viewpoint of ease of synthesis, n in the formula (1) is preferably 1.
  • the molecular weight of component (A) is preferably 500 to 100,000, more preferably 1,000 to 30,000, even more preferably 1. 000 to 10,000.
  • component (A) for example, various known polyarylene sulfide production methods (polycondensation with aromatic halogen compounds and sodium sulfide, oxidative polymerization of aromatic thiol compounds or aromatic disulfide compounds, etc.) are applied to naphthalene derivatives. It can be synthesized by Polymers having hydroxy groups can be synthesized by applying various known polyarylene sulfide production methods to naphthol derivatives with protected hydroxy groups, and then deprotecting some or all of the protecting groups. good.
  • an oxidative polymerization method is preferable, and in particular, from the viewpoint that it can be produced at room temperature and normal pressure without using a metal catalyst, the quinone described in Patent Document 5 and Patent Document 6
  • An oxidative polymerization method using an oxidizing agent and an acid is preferably used.
  • an aromatic thiol compound that may contain a methyl group, an ethyl group, a methoxy group, an ethoxy group, or a hydroxy group, or an aromatic thiol compound that may contain a methyl group, an ethyl group, a methoxy group, or an ethoxy group.
  • a method of oxidative polymerization using an aromatic disulfide compound that may contain a hydroxy group as a monomer using a quinone oxidizing agent and an acid, or an aromatic thiol compound containing a protected hydroxy group or a protected hydroxy group.
  • An example of a method is to perform oxidative polymerization using an aromatic disulfide compound containing as a monomer using a quinone oxidizing agent and an acid, and then deprotect some or all of the protecting groups.
  • the protected hydroxy group is not particularly limited as long as polymerization proceeds, but from the viewpoint of stability that does not interfere with quinone oxidizing agents or acids, an alkoxy group is preferable, a methoxy group or an ethoxy group is more preferable, and in the case of a methoxy group is particularly preferable since the deprotection reaction can proceed more easily.
  • the alkoxy group can be converted into a hydroxy group by removing the alkyl group by applying an acid or the like.
  • the acid include trisubstituted boron compounds (boron tribromide, etc.) and Lewis acids such as aluminum chloride, and thiol compounds (dodecanethiol, etc.) and Bronsted acids such as hydrogen bromide. It is not particularly limited as long as it is an acid that can be converted into. All of the protecting groups may be removed or some may remain. Optical properties and solubility can be controlled by appropriately adjusting the deprotection rate.
  • the above formula (2) (However, the disulfide monomer represented by the above formula (2a) is excluded.) and/or the thiol monomer represented by the above formula (3) (However, the thiol represented by the above formula (3a) is (excluding monomers) can be suitably used.
  • a disulfide monomer represented by the following formula (18) and/or a disulfide monomer represented by the following formula (19) is synthesized.
  • Thiol monomers can be suitably used.
  • the monomers used in the synthesis of component (A) may be used alone or in combination of two or more. From the viewpoint of adjusting optical properties and solubility in organic solvents, disulfide monomers not represented by the above formula (2) and the above formula (18) (for example, the following formulas (20) to (38)) may be used as necessary. ) or thiol monomers not represented by the formula (3) or formula (19) (for example, thiol monomers represented by the following formulas (39) to (57)). ) may be used. That is, the polymer only needs to contain at least one structural unit represented by the above formula (1) or the above formula (4), and may be a homopolymer or a copolymer. .
  • the polymer is a copolymer
  • its repeating structure is not particularly limited, and it may be any of an alternating copolymer, a block copolymer, a gradient copolymer, and a random copolymer. Further, the polymer may be branched depending on the polymerization conditions.
  • Component (B) is not particularly limited as long as it is an organic solvent that dissolves component (A), but an organic solvent having a melting point of 15° C. or lower and a boiling point of 85° C. or higher is particularly desirable.
  • the melting point and boiling point refer to those under 1 atmosphere. Since the melting point is 15° C. or lower, the resin composition has excellent handling properties at room temperature.
  • the melting point is preferably 10°C or lower, more preferably 5°C or lower, from the viewpoint of storage stability in a cool place. Further, the lower limit of the melting point is not particularly limited, but is preferably -150°C or higher, for example.
  • the boiling point is 85° C.
  • the boiling point is preferably 100°C or higher, more preferably 115°C or higher, particularly from the viewpoint of easily forming a homogeneous coating film. Further, from the viewpoint of organic solvent removability, the upper limit of the boiling point is preferably 300°C or less, more preferably 250°C or less, and even more preferably 220°C or less.
  • component (B) examples include methylcyclohexane, ethylcyclohexane, n-heptane, toluene, o-xylene, m-xylene, mesitylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, anisole, phenetol, di- n-propyl ether, di-n-butyl ether, diisobutyl ether, di-n-pentyl ether, diisopentyl ether, di-n-hexyl ether, n-butyl ethyl ether, methyl-n-pentyl ether, cyclopentyl methyl ether, Tetrahydropyran, 1,3-dioxane, 1,4-dioxane, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 1-pentan
  • Component (B) may include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene, from the viewpoint of improving the leveling properties of the coating film formed by applying the resin composition onto a substrate.
  • the component (B) may be used alone or in combination of two or more. In addition, it may be mixed with a solvent other than component (B) as appropriate. In that case, the content of component (B) is 50% to 100% by mass of the entire solvent including component (B) and other solvents. It is preferably 60% to 100% by weight, even more preferably 70% to 100% by weight.
  • the other solvents include methanol, ethanol, 2-propanol, dichloromethane, 1,2-dichloroethane, chloroform, acetone, 2-butanone, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), ethyl acetate, and Examples include acetonitrile.
  • the resin composition of the present invention may further contain (C) a polyfunctional epoxy compound for the purpose of improving chemical resistance.
  • the component (C) is not particularly limited as long as it is a compound having at least two oxirane rings in the molecule, and for example, the following products and compounds can be used.
  • TEPIC (registered trademark)-G, TEPIC-L, TEPIC-VL, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP (manufactured by Nissan Chemical Co., Ltd.), Marproof (registered trademark) G- 01100, G-0105SA, G-0130SF, G-0130SP, G-0150M, G-0250SF, G-0250SP, G-05100, G-2050M, G-017581.
  • OGSOL registered trademark
  • PG-100 CG-500, EG-200, EG-280 (manufactured by Osaka Gas Chemical Co., Ltd.)
  • GTR-1800 registered trademark
  • EPICLON registered trademark 830, 830-S, 835, 840, 840-S, 850, 850-S, 850-LC, HP-820 (manufactured by Yakuhin Co., Ltd.)
  • DENACOL registered trademark
  • EX-201 EX-211, EX-212, EX-252, EX-810, EX-811, EX-821, EX-830 , EX-832, EX-841, EX-850, EX-851, EX-861, EX-920, EX-931, EX-991L, EX-313, EX-314 , EX-321, EX-321L, EX-411, EX-421, EX-512, EX-521, EX-612, E
  • the component (C) may be used alone or in combination of two or more.
  • the content of component (C) is preferably 5 parts by mass to 50 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of component (A). parts to 30 parts by mass.
  • the resin composition of the present invention may optionally contain a surfactant for the purpose of improving coating properties.
  • surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether and polyoxyethylene Polyoxyethylene alkylaryl ethers such as nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan triolate, and sorbitan tri Sorbitan fatty acid esters such as stearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triolate, polyoxyethylene
  • Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters; EFTOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F-171 , F-173, R-30, R-40, R-40-LM (manufactured by DIC Corporation), Florado FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon (registered trademark) SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation), FTX-206D, FTX-212D, FTX- 218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FT
  • the content of the surfactant is preferably 0.001 parts by mass to 3 parts by mass, more preferably 0.005 parts by mass based on 100 parts by mass of total solids. part to 1 part by weight, even more preferably 0.01 part to 0.5 part by weight.
  • the resin composition of the present invention may optionally contain curing aids, antioxidants, light stabilizers (HALS), ultraviolet absorbers, plasticizers, adhesion aids, etc., as long as the effects of the present invention are not impaired.
  • the composition may further include an agent.
  • the method for preparing the resin composition of the present invention is not particularly limited, but includes, for example, a method of mixing components (A) and (B), and optionally component (C) and other components to form a uniform solution. It will be done. Further, if necessary, the obtained solution may be filtered using a filter with a pore size of 0.1 ⁇ m to 10 ⁇ m.
  • the solid content concentration of the resin composition thus obtained is usually 1% by mass to 50% by mass from the viewpoint of applicability to a substrate.
  • a suitable method such as a spinner or a coater is applied onto a base material (for example, a PET film, a TAC film, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films or color filters are formed on the surface).
  • a resin film is produced by baking using a heating means such as a hot plate or an oven.
  • the baking conditions are appropriately selected from baking temperatures of 50° C. to 300° C. and baking times of 0.1 minutes to 360 minutes. Baking when producing the resin film may be performed in two or more steps.
  • the thickness of the resin film formed is 0.001 ⁇ m to 1,000 ⁇ m, preferably 0.01 ⁇ m to 100 ⁇ m, and more preferably 0.1 ⁇ m to 10 ⁇ m.
  • a resist is applied onto the resin film produced through the above [Resin film production method], the resist is exposed through a predetermined mask, and if necessary, post-exposure heating (PEB) is performed, and further alkaline development, A resist pattern is formed on the resin film by rinsing and drying.
  • PEB post-exposure heating
  • the resist pattern is reflowed by heat treatment to form a lens pattern.
  • the resin film below the lens pattern is etched back, and the shape of the lens pattern is transferred to the resin film, thereby producing a microlens.
  • the precipitate generated by the dropping was collected and washed with ethanol, methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water in this order.
  • the precipitate generated by the dropping was collected, washed in the order of methanol, a 3% by mass potassium hydroxide aqueous solution, and pure water, and then dried at 80°C under reduced pressure to obtain the precipitate expressed by the formula (1ca) above.
  • 5.8 g of the polymer of the present invention [poly(2-methoxynaphthylene sulfide)] containing a structural unit of The weight average molecular weight M W of the obtained polymer was 1,300 in terms of polystyrene.
  • ⁇ Polymer synthesis example 3> 4.6 g (20 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 0.8 g (7 mmol) of trifluoroacetic acid, and 7 mL of chloroform were placed in a flask containing a stirring bar and stirred. Thereafter, 5.6 g (20 mmol) of the monomer obtained in Monomer Synthesis Example 2 was added and stirred for 40 hours. Next, 73 mL of chloroform was added to the reaction solution, and the precipitate was removed by filtration, and then the filtrate was dropped into 800 mL of stirred ethanol/12N hydrochloric acid 95/5 (volume ratio).
  • the precipitate generated by the dropping is collected, washed in the order of methanol, a 3% by mass aqueous potassium hydroxide solution, and pure water, and then dried at 80°C under reduced pressure to obtain a structural unit represented by the following formula. 4 g of a polymer containing [poly(2-methoxyphenylene sulfide)] was obtained.
  • the weight average molecular weight M W of the obtained polymer was 3,000 in terms of polystyrene.
  • the precipitate generated by the dropping is collected, washed in the order of methanol, a 3% by mass potassium hydroxide aqueous solution, and pure water, and then dried at 80°C under reduced pressure to form two types represented by the following formulas. 3.0 g of the copolymer of the present invention [poly(2-naphthylene sulfide/2-methoxyphenylene sulfide)] containing the structural unit was obtained. The weight average molecular weight M W of the obtained copolymer was 1,300 in terms of polystyrene.
  • the precipitate generated by the dropping is collected, washed in the order of methanol, a 3% by mass potassium hydroxide aqueous solution, and pure water, and then dried at 80°C under reduced pressure to form two types represented by the following formulas.
  • 2.0 g of the copolymer of the present invention [poly(2-methyl-1-naphthylene sulfide/2-methoxyphenylene sulfide)] containing the structural unit was obtained.
  • the weight average molecular weight M W of the obtained copolymer was 1,700 in terms of polystyrene.
  • Example 2 A resin composition (solid content concentration: 18% by mass) was obtained in the same manner as in Example 1, except that the copolymer obtained in Polymer Synthesis Example 6 was used as the component (A).
  • Example 3 A resin composition (solid content concentration: 18% by mass) was obtained in the same manner as in Example 1 except that the copolymer obtained in Polymer Synthesis Example 8 was used as the component (A).
  • a resist solution THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied onto a silicon wafer using a spin coater, and heated on a hot plate at 90°C for 1.5 minutes, at 110°C for 1.5 minutes, and then at 180°C. C. for 1 minute to form a resist film with a thickness of 1 ⁇ m.
  • the resist film was dry etched using a dry etching apparatus RIE-10NR (manufactured by Samco Co., Ltd.) (etching gas: CF 4 ), and the dry etching rate of the resist film was measured.
  • each of the resin compositions prepared in Examples 1 to 3 and Comparative Example 1 was applied onto a silicon wafer using a spin coater, and baked on a hot plate at 100° C. for 1 minute. Thereafter, it was baked at 200° C. for 5 minutes to form a resin film with a thickness of 1 ⁇ m, and the dry etching rate was similarly measured. Then, the dry etching rate of the resin films obtained from the resin compositions prepared in Examples 1 to 3 and Comparative Example 1 with respect to the resist film was calculated. The results are shown in Table 1.
  • the lens pattern is removed as an etching mask. After dry-etching the resin film until the end, the width of the formed microlens was measured.
  • the resin film obtained from the resin composition containing the polynaphthylene sulfide resin of the present invention has a high refractive index of 1.75 or more at a wavelength of 550 nm and exhibits excellent lens moldability by an etch-back method. was confirmed. From the above results, the polymer and the resin composition for optical lenses of the present invention are useful for optical lenses, especially microlenses.

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Abstract

L'invention concerne un polymère qui a à la fois un indice de réfraction élevé et une excellente aptitude au moulage de lentille et contient une unité structurale représentée par la formule (1) (cependant, une unité structurale représentée par la formule (1a) est exclue). (Dans la formule, X représente chacun indépendamment un groupe méthyle, un groupe éthyle, un groupe méthoxy, un groupe éthoxy ou un groupe hydroxy, et n représente un nombre entier de 1 à 6.)
PCT/JP2023/011733 2022-05-18 2023-03-24 Polymère et composition de résine pour lentille optique WO2023223670A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570593A (ja) * 1991-03-15 1993-03-23 Otsuka Chem Co Ltd 芳香族ポリチオエーテルの製造方法
JPH0948853A (ja) * 1995-08-08 1997-02-18 Res Dev Corp Of Japan ポリ（アリーレンスルホニウム塩）化合物
CN114181360A (zh) * 2021-12-08 2022-03-15 南京工业大学 一种超声波刺激响应聚氨酯及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0570593A (ja) * 1991-03-15 1993-03-23 Otsuka Chem Co Ltd 芳香族ポリチオエーテルの製造方法
JPH0948853A (ja) * 1995-08-08 1997-02-18 Res Dev Corp Of Japan ポリ（アリーレンスルホニウム塩）化合物
CN114181360A (zh) * 2021-12-08 2022-03-15 南京工业大学 一种超声波刺激响应聚氨酯及其制备方法

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